CN105542228A - Preparation method of functionalized nano-silica based on graphene - Google Patents

Preparation method of functionalized nano-silica based on graphene Download PDF

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CN105542228A
CN105542228A CN201610071005.2A CN201610071005A CN105542228A CN 105542228 A CN105542228 A CN 105542228A CN 201610071005 A CN201610071005 A CN 201610071005A CN 105542228 A CN105542228 A CN 105542228A
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graphene
nano silicon
suspension
dioxide
graphene oxide
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刘岚
林勇
陈松
袁雪
罗远芳
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to PCT/CN2016/109339 priority patent/WO2017128873A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a preparation method of functionalized nano-silica based on graphene. The method comprises the steps of, firstly, primarily preparing to obtain graphite oxide by using a modified hummer method; secondly, preparing by using vibration and assisted ultrasonic, thus obtaining an evenly dispersed graphene oxide and nano-silica suspension liquid; thirdly, preparing silane grafted oxidized graphene and nano-silica by using a surface modification method; lastly, preparing by using electrostatic assembling and chemical reduction, thus obtaining a graphene-nano-silica hybrid material. The method is simple and effective, solves the problems that graphene layers are stacked and the nan-silica is agglomerated seriously, and has potential application values.

Description

A kind of preparation method of the function nano silicon-dioxide based on Graphene
Technical field
The present invention relates to the preparing technical field of advanced function material, be specifically related to a kind of preparation method of the function nano silicon-dioxide based on Graphene.
Background technology
British scientist AndrewGeim in 2004 etc. utilize adhesive tape micromechanics to peel off highly oriented pyrolytic graphite, find and prepare Graphene.Graphene has the mechanical property (modulus is about 1100GPa, and breaking tenacity is about 130GPa) of superelevation, high thermal conductivity (about 5000W/ (m K)), high electron mobility (up to 2 × 10 6cm 2v -1s -1), high-specific surface area (can reach 2630m 2/ g) and high obstructing performance etc.The unique physical that Graphene shows and electricity
Sub-feature, makes it have a wide range of applications potentiality in fields such as nano-device, matrix material, sensor, energy storage materials.Meanwhile, the preparation method of Graphene mainly comprises mechanically peel method, solution liquid phase stripping method, epitaxial growth method, chemical Vapor deposition process and redox graphene method etc.Compare additive method, redox graphene method has magnanimity and cheap advantage, makes it in the magnanimity applied researcies such as polymer composites, provide chance.But, due in reduction process, due to Graphene, there is very high surface energy and strong π-π interacts, easily in solid phase or usual vehicle, all occur irreversible agglomeration.Therefore, cause based on the function nano hybrid material of Graphene and study widely.This matrix material by Graphene and other nano particle hybridizations has well dispersed and interface performance in the polymer.Meanwhile, hybrid structure can improve the over-all properties of matrix material significantly.In addition, nano silicon, initial size is generally 10-40nm, has the excellent properties such as polymolecularity, chemical stability is good, high temperature resistant, electrical insulating property is good.Meanwhile, nano silicon is a kind of excellent rubber-reinforcing filler, significantly can improve the dynamic and static mechanics performance of matrix material.Graphene-nano silicon dioxide hybridization material not only can improve the dispersiveness of Graphene, nano silicon respectively, is conducive to the potential range of application expanding Graphene further simultaneously.
Summary of the invention
The present invention first by modification Hummer legal system for the high graphite oxide of degree of oxidation.Surface graft modification prepares graphene oxide and nanometer titanium dioxide silicon suspension in organic solvent.Then, Graphene-nano silicon dioxide hybridization material is prepared by electrostatic assembly.
First the present invention by modification Hummer method, tentatively prepares graphite oxide.Secondly, vibration and assisting ultrasonic is adopted to prepare homodisperse graphene oxide and nanometer titanium dioxide silicon suspension.Then surface-modification method is adopted to prepare Silane Grafted graphene oxide and nano silicon.Finally, electrostatic assembly and chemical reduction is adopted to prepare Graphene-nano silicon dioxide hybridization material: namely first graphene oxide suspension and nanometer titanium dioxide silicon suspension to be mixed in high-speed stirring, the silicon-dioxide of electronegative graphene oxide lamella and positively charged adsorbs down mutually mutually at electrostatic, and nanometer silicon dioxide particle is carried on graphene oxide lamella surface; Add reductive agent, graphene oxide is effectively reduced, obtain Graphene-nano silicon dioxide hybridization material, achieve the serious agglomeration of the heap superimposition nano silicon hindering graphene sheet layer.
Object of the present invention is realized by following scheme:
Based on a preparation method for the function nano silicon-dioxide of Graphene, comprise following concrete steps:
(1) graphite oxide powder is prepared: adopt modification Hummers method to prepare jonquilleous graphite oxide powder.
(2) graphene oxide suspension and nanometer titanium dioxide silicon suspension is prepared: the graphite oxide powder simple oscillation obtained in step (1) and assisting ultrasonic are disperseed in organic solvent, obtain the graphene oxide suspension of yellowish brown.Meanwhile, by nano silica powder ultrasonic disperse in organic solvent, obtain amination nanometer titanium dioxide silicon suspension.
(3) functional graphene oxide suspension is prepared: by the graphene oxide suspension obtained in step (2), add active modifier, react under nitrogen environment, obtain functional graphene oxide suspension.
(4) prepare amination nanometer titanium dioxide silicon suspension: by the nanometer titanium dioxide silicon suspension obtained in step (2), add amino silane modified dose of reaction, obtain amination nanometer titanium dioxide silicon suspension.
(5) Graphene-nano silicon dioxide hybridization material is prepared: first mixed with modified manometer silicon dioxide uniform suspension by step (3) modified graphene oxide suspension, natural subsidence, washing; Obtain khaki color graphene oxide-nano silicon dioxide hybridization material.Above-mentioned hybrid material is scattered in organic solution again, adds a certain amount of hydrazine hydrate reduction, adopt ethanol and water washing for several times, dry, obtain the function nano silicon-dioxide based on Graphene of grey.
Further, described organic solvent is following any one: methyl alcohol, ethanol, acetone, toluene, tetrahydrofuran (THF), N-METHYLFORMAMIDE, dimethyl sulfoxide (DMSO) and water;
Further, the starting point concentration of described graphene oxide suspension is 0.1 ~ 2mg/mL; The starting point concentration of nanometer titanium dioxide silicon suspension is 3 ~ 50mg/mL; The solvent of described each step may be the same or different;
Further, described active modifier is following any one: γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, γ-mercaptopropyl trimethoxysilane and gamma-mercaptopropyltriethoxysilane;
Further, the mass ratio of described graphene oxide and active modifier is 1:0.5 ~ 1:10; Temperature of reaction is 50 ~ 90 DEG C; Reaction times is 10 ~ 24h;
Further, described amino silane modified dose is following any one: γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane and g-aminopropyl trimethoxysilane;
Further, the mass ratio of described nano silicon and amino silane modified dose is 1:0.5 ~ 1:20;
Further, described amino modified temperature of reaction is 60 ~ 100 DEG C, and the reaction times is 2 ~ 24h;
Further, the mass ratio of described functional graphene oxide and amination silicon-dioxide is 1:5 ~ 1:50.
Further, the mass ratio of described hydrazine hydrate and graphene oxide-silicon dioxide hybrid materials is 1:150 ~ 1:300.
Compared with prior art, the present invention has following advantage and technique effect:
(1) prepare the technique simple possible of Graphene-nano silicon dioxide hybridization material, reaction conditions is gentle, is convenient to carry out scale operation;
(2) the method can suppress the reunion of Graphene and nano silicon mutually, meanwhile, significantly enhances the interface cohesion of hybrid material and rubber matrix, is conducive to the over-all properties improving rubber composite.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of Graphene-nano silicon dioxide hybridization material prepared by each embodiment.
Fig. 2 is the TEM figure of Graphene-nano silicon dioxide hybridization material prepared by each embodiment.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
embodiment 1:
(1) graphite oxide is prepared: adopt modification Hummers method to prepare jonquilleous graphite oxide powder.
(2) graphene oxide and nanometer titanium dioxide silicon suspension is prepared: the graphite oxide powder simple oscillation obtained in step (1) and assisting ultrasonic are disperseed in ethanol, obtain the graphene oxide suspension that starting point concentration is 0.5mg/mL yellowish brown.Meanwhile, by nano silica powder ultrasonic disperse in ethanol, obtain the silica suspension that starting point concentration is 5mg/ml.
(3) functional graphene oxide is prepared: by the 200mL graphene oxide suspension obtained in step (2), add 0.1g γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, under nitrogen environment, 60 DEG C of reaction 10h, obtain functional graphene oxide.
(4) amination nano silicon is prepared: by the 100mL nanometer titanium dioxide silicon suspension obtained in step (2), add 0.5g γ-aminopropyl triethoxysilane, at 70 DEG C, react 10h, obtain amination nano silicon.
(5) prepare Graphene-nano silicon dioxide hybridization material: first mixed with modified manometer silicon dioxide suspension 500r/min high-speed stirring by step (3) modified graphene oxide suspension, natural subsidence, adopt ethanol and water washing for several times.Obtain graphene oxide-nano silicon dioxide hybridization material.Again be scattered in water by above-mentioned hybrid material, add 4mg hydrazine hydrate reduction 10h, with water repeated washing several, 90 DEG C of dry 24h subsequently, obtain the function nano silicon-dioxide based on Graphene of grey.
By the functionalization graphene that extracting obtains in (3), the percentage of grafting calculating γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane in conjunction with thermogravimetric analysis is 12.6%.In (4) by the amination nano silicon that extracting obtains, the percentage of grafting calculating γ-aminopropyl triethoxysilane in conjunction with thermogravimetric analysis is 5.1%.(5) in, Graphene accounts for the mass percent of Graphene-nano silicon dioxide hybridization material is 7.81%.
embodiment 2:
(1) graphite oxide is prepared: adopt modification Hummers method to prepare jonquilleous graphite oxide powder.
(2) graphene oxide and nanometer titanium dioxide silicon suspension is prepared: the graphite oxide powder simple oscillation obtained in step (1) and assisting ultrasonic are disperseed in ethanol, obtain the graphene oxide suspension that starting point concentration is 0.5mg/ml yellowish brown.Meanwhile, by nano silica powder ultrasonic disperse in ethanol, obtain the silica suspension that starting point concentration is 10mg/ml.
(3) functional graphene oxide is prepared: by the 200mL graphene oxide suspension obtained in step (2), add 0.1g γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, under nitrogen environment, 60 DEG C of reaction 16h, obtain functional graphene oxide.
(4) amination nano silicon is prepared: by the 100mL nanometer titanium dioxide silicon suspension obtained in step (2), add 1g γ-aminopropyl triethoxysilane, at 70 DEG C, react 16h, obtain amination nano silicon.
(5) prepare Graphene-nano silicon dioxide hybridization material: first mixed with modified manometer silicon dioxide suspension 500r/min high-speed stirring by step (3) modified graphene oxide suspension, natural subsidence, adopt ethanol and water washing for several times.Obtain graphene oxide-nano silicon dioxide hybridization material.Above-mentioned hybrid material is scattered in water again, adds 8mg hydrazine hydrate reduction 10h, with water repeated washing for several times, dry 24h at 90 DEG C, obtains the function nano silicon-dioxide based on Graphene of grey subsequently.
By the functionalization graphene that extracting obtains in (3), the percentage of grafting calculating γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane in conjunction with thermogravimetric analysis is 19.4%.In (4) by the amination nano silicon that extracting obtains, the percentage of grafting calculating γ-aminopropyl triethoxysilane in conjunction with thermogravimetric analysis is 9.6%.(5) in, Graphene accounts for the mass percent of Graphene-nano silicon dioxide hybridization material is 3.46%.
embodiment 3:
(1) graphite oxide is prepared: adopt modification Hummers method to prepare jonquilleous graphite oxide powder.
(2) graphene oxide and nanometer titanium dioxide silicon suspension is prepared: the graphite oxide powder simple oscillation obtained in step (1) and assisting ultrasonic are disperseed in ethanol, obtain the graphene oxide suspension that starting point concentration is 0.5mg/ml yellowish brown.Meanwhile, by nano silica powder ultrasonic disperse in ethanol, obtain the silica suspension that starting point concentration is 50mg/ml.
(3) functional graphene oxide is prepared: by the 200mL graphene oxide suspension obtained in step (2), add 0.1g γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, under nitrogen environment, 60 DEG C of reaction 24h, obtain functional graphene oxide.
(4) amination nano silicon is prepared: by the 100mL nanometer titanium dioxide silicon suspension obtained in step (2), add 5g γ-aminopropyl triethoxysilane, at 70 DEG C, react 24h, obtain amination nano silicon.
(5) prepare Graphene-nano silicon dioxide hybridization material: first mixed with modified manometer silicon dioxide suspension 500r/min high-speed stirring by step (3) modified graphene oxide suspension, natural subsidence, adopt ethanol and water washing for several times.Obtain graphene oxide-nano silicon dioxide hybridization material.Again be scattered in water by above-mentioned hybrid material, add 34mg hydrazine hydrate reduction 10h, with water repeated washing several, 90 DEG C of dry 24h subsequently, obtain the function nano silicon-dioxide based on Graphene of grey.
By the functionalization graphene that extracting obtains in (3), the percentage of grafting calculating γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane in conjunction with thermogravimetric analysis is 28.9%.In (4) by the amination nano silicon that extracting obtains, the percentage of grafting calculating γ-aminopropyl triethoxysilane in conjunction with thermogravimetric analysis is 16.4%.(5) in, Graphene accounts for the mass percent of Graphene-nano silicon dioxide hybridization material is 0.85%.
embodiment 4:
(1) graphite oxide is prepared: adopt modification Hummers method to prepare jonquilleous graphite oxide powder.
(2) graphene oxide and nanometer titanium dioxide silicon suspension is prepared: the graphite oxide powder simple oscillation obtained in step (1) and assisting ultrasonic are disperseed in ethanol, obtain the graphene oxide suspension that starting point concentration is 0.1mg/ml yellowish brown.Meanwhile, by nano silica powder ultrasonic disperse in ethanol, obtain the silica suspension that starting point concentration is 5mg/ml.
(3) functional graphene oxide is prepared: by the 200mL graphene oxide suspension obtained in step (2), add 0.02g γ-methacryloxypropyl trimethoxy silane, under nitrogen environment, 60 DEG C of reaction 24h, obtain functional graphene oxide.
(4) amination nano silicon is prepared: by the 100mL nanometer titanium dioxide silicon suspension obtained in step (2), add 1gN-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, at 70 DEG C, react 24h, obtain amination nano silicon.
(5) prepare Graphene-nano silicon dioxide hybridization material: first mixed with modified manometer silicon dioxide suspension 500r/min high-speed stirring by step (3) modified graphene oxide suspension, natural subsidence, adopt ethanol and water washing for several times.Obtain graphene oxide-nano silicon dioxide hybridization material.Again be scattered in water by above-mentioned hybrid material, add 3.5mg hydrazine hydrate reduction 10h, with water repeated washing several, 90 DEG C of dry 24h subsequently, obtain the function nano silicon-dioxide based on Graphene of grey.
By the functionalization graphene that extracting obtains in (3), the percentage of grafting calculating γ-methacryloxypropyl trimethoxy silane in conjunction with thermogravimetric analysis is 22.6%.In (4) by the amination nano silicon that extracting obtains, the percentage of grafting calculating N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane in conjunction with thermogravimetric analysis is 14.8%.(5) in, Graphene accounts for the mass percent of Graphene-nano silicon dioxide hybridization material is 1.59%.
embodiment 5:
(1) graphite oxide is prepared: adopt modification Hummers method to prepare jonquilleous graphite oxide powder.
(2) graphene oxide and nanometer titanium dioxide silicon suspension is prepared: the graphite oxide powder simple oscillation obtained in step (1) and assisting ultrasonic are disperseed in ethanol, obtain the graphene oxide suspension that starting point concentration is 2mg/ml yellowish brown.Meanwhile, by nano silica powder ultrasonic disperse in ethanol, obtain the silica suspension that starting point concentration is 50mg/ml.
(3) functional graphene oxide is prepared: by the 200mL graphene oxide suspension obtained in step (2), add 0.4g γ-methacryloxypropyl trimethoxy silane, under nitrogen environment, 60 DEG C of reaction 24h, obtain functional graphene oxide.
(4) amination nano silicon is prepared: by the 100mL nanometer titanium dioxide silicon suspension obtained in step (2), add 5gN-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, at 70 DEG C, react 24h, obtain amination nano silicon.
(5) prepare Graphene-nano silicon dioxide hybridization material: first mixed with modified manometer silicon dioxide suspension 500r/min high-speed stirring by step (3) modified graphene oxide suspension, natural subsidence, adopt ethanol and water washing for several times.Obtain graphene oxide-nano silicon dioxide hybridization material.Again be scattered in water by above-mentioned hybrid material, add 36mg hydrazine hydrate reduction 10h, with water repeated washing several, 90 DEG C of dry 24h subsequently, obtain the function nano silicon-dioxide based on Graphene of grey.
By the functionalization graphene that extracting obtains in (3), the percentage of grafting calculating γ-methacryloxypropyl trimethoxy silane in conjunction with thermogravimetric analysis is 26.1%.In (4) by the amination nano silicon that extracting obtains, the percentage of grafting calculating N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane in conjunction with thermogravimetric analysis is 17.2%.(5) in, Graphene accounts for the mass percent of Graphene-nano silicon dioxide hybridization material is 3.24%.
As can be seen from Figure 1, after chemical reduction, there is not the characteristic diffraction peak in graphite oxide [001] face in the XRD figure spectrum of Graphene-nano silicon dioxide hybridization material, illustrate that graphene oxide is successfully reduced.Meanwhile, the XRD figure spectrum of the hybrid material prepared by each embodiment is very identical with the collection of illustrative plates of pure nano silicon, and the graphite peaks not occurring the stacking reunion of Graphene and formed.Therefore, after hybrid modification, nano silicon can suppress the reunion of graphene film interlayer effectively.Simultaneously, also shown in observing as transmission electron microscope (TEM) (Fig. 2), nano silicon load and graphenic surface and interlayer, form the hybrid of self-assembly, because modified graphene oxide is different from the proportioning of improved silica, the TEM photo of the Graphene prepared by each embodiment-SiO 2 hybrid thing is distinguished to some extent, when the ratio of improved silica is less, can find out, silica dioxide granule is dispersed in graphene sheet layer interlayer and surface (as embodiment 1 ~ 3), when the ratio of improved silica increases, the particulate load of a large amount of reunion is in graphene sheet layer surface (as embodiment 4 and embodiment 5), therefore, the hybrid material of ideal structure can be obtained by the proportioning regulating and controlling modified graphene oxide and improved silica, namely the stacking of Graphene can either be hindered, also the reunion of nano silicon can be suppressed.

Claims (10)

1. based on a preparation method for the function nano silicon-dioxide of Graphene, it is characterized in that, comprise following concrete steps:
(1) graphite oxide powder is prepared: adopt modification Hummers method to prepare jonquilleous graphite oxide powder;
(2) graphene oxide suspension and nanometer titanium dioxide silicon suspension is prepared: graphite oxide powder process vibration step (1) obtained and ultrasonic disperse in a solvent, obtain the graphene oxide suspension of yellowish brown; Meanwhile, by nano silica powder ultrasonic disperse in solvent, obtain nanometer titanium dioxide silicon suspension;
(3) functional graphene oxide suspension is prepared: add in active modifier by the graphene oxide suspension that step (2) obtains, react under nitrogen environment, obtain functional graphene oxide suspension;
(4) amination nanometer titanium dioxide silicon suspension is prepared: added in nanometer titanium dioxide silicon suspension step (2) obtained in amino silane modified dose and react, obtain amination nanometer titanium dioxide silicon suspension;
(5) Graphene-nano silicon dioxide hybridization material is prepared: the amination nano silicon uniform suspension that the functional graphene oxide suspension first step (3) obtained and step (4) obtain mixes, natural subsidence, washing; Obtain khaki color graphene oxide-nano silicon dioxide hybridization material; Be scattered in solvent by above-mentioned hybrid material, add hydrazine hydrate reduction, washing is dry, obtains the function nano silicon-dioxide based on Graphene of grey.
2. the preparation method of a kind of function nano silicon-dioxide based on Graphene according to claim 1, it is characterized in that, the above solvent is following any one: methyl alcohol, ethanol, acetone, toluene, tetrahydrofuran (THF), N-METHYLFORMAMIDE, dimethyl sulfoxide (DMSO) and water; The solvent of described each step may be the same or different.
3. the preparation method of a kind of function nano silicon-dioxide based on Graphene according to claim 1, is characterized in that, the starting point concentration of step (2) described graphene oxide suspension is 0.1 ~ 2mg/ml; The starting point concentration of nanometer titanium dioxide silicon suspension is 3 ~ 50mg/ml.
4. the preparation method of a kind of function nano silicon-dioxide based on Graphene according to claim 1, it is characterized in that, active modifier described in step (3) is following any one: γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, γ-mercaptopropyl trimethoxysilane and gamma-mercaptopropyltriethoxysilane.
5. the preparation method of a kind of function nano silicon-dioxide based on Graphene according to claim 1, is characterized in that, the mass ratio of step (3) described graphene oxide and active modifier is 1:0.5 ~ 1:10; Temperature of reaction is 50 ~ 90 DEG C; Reaction times is 10 ~ 24h.
6. the preparation method of a kind of function nano silicon-dioxide based on Graphene according to claim 1, it is characterized in that, amino silane modified dose described in step (4) is following any one: γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane and g-aminopropyl trimethoxysilane.
7. the preparation method of a kind of function nano silicon-dioxide based on Graphene according to claim 1, is characterized in that, the mass ratio of step (4) described nano silicon and amino silane modified dose is 1:0.5 ~ 1:20.
8. the preparation method of a kind of function nano silicon-dioxide based on Graphene according to claim 1, it is characterized in that, the amino modified temperature of reaction described in step (4) is 60 ~ 100 DEG C, and the reaction times is 2 ~ 24h.
9. the preparation method of a kind of function nano silicon-dioxide based on Graphene according to claim 1, is characterized in that, the functional graphene oxide described in step (5) and the mass ratio of amination nano silicon are 1:5 ~ 1:50.
10. the preparation method of a kind of function nano silicon-dioxide based on Graphene according to claim 1, is characterized in that, the hydrazine hydrate described in step (5) and the mass ratio of graphene oxide-nano silicon dioxide hybridization material are 1:150 ~ 1:300.
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